CN108796443A - A kind of nitridation of hot die steel low-temperature plasma plates compounding method with cathode ion - Google Patents

A kind of nitridation of hot die steel low-temperature plasma plates compounding method with cathode ion Download PDF

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Publication number
CN108796443A
CN108796443A CN201810694421.7A CN201810694421A CN108796443A CN 108796443 A CN108796443 A CN 108796443A CN 201810694421 A CN201810694421 A CN 201810694421A CN 108796443 A CN108796443 A CN 108796443A
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China
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temperature plasma
die steel
low
hot die
compounding method
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CN201810694421.7A
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Chinese (zh)
Inventor
孔德军
赵文
王文昌
李佳红
陈海翔
蔡金龙
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Changzhou University
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C23C8/38—Treatment of ferrous surfaces

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention relates to the surface modification treatment fields of hot die steel, disclose a kind of compounding method of surface of hot die steel low-temperature plasma nitridation-cathode ion plating.The processing method will be spread and coating technology is combined, depositing Al CrN coatings on the basis of low-temperature plasma nitration case, it is not high so as to avoid nitration case mechanical property when single progress nitrogen treatment, the problem of cannot be satisfied mold work demand, it also avoids when single progresss coating treatment that coating bearing capacity is low simultaneously, lacks the problem of support is easy to fail.The present invention is effectively improved hardness, wearability, inoxidizability and the thermal stability of mold, so that mold is suitable for extreme operating mode, is conducive to production application.

Description

A kind of nitridation of hot die steel low-temperature plasma plates compounding method with cathode ion
Technical field
The present invention relates to surface of hot die steel modification treatment technology fields, refer in particular to surface of hot die steel low-temperature plasma The surface treatment method of nitridation-cathode ion plating, to solve diaphragm failure caused by single one physical vapor deposition and single etc. The relatively low problem of hardness caused by ionic nitriding, belongs to material surface modifying composite treatment technology.
Background technology
Mold, in occupation of very important status, is that the important process of part forming equips it during part forming One.Because being frequently accompanied by the extreme situations such as high temperature, humidity, impact and severe friction in its course of work, mold materials often need There are the performances such as good wearability, corrosion resistance, high-temperature behavior and cold & heat fatigue resisting.To improve material surface Can, improve material surface and deteriorate problem, the steps necessary being processed into being produced for mold is modified to material surface.When right Die surface carry out nitrogen treatment when, nitration case makes material mechanical performance be improved, but via nitride processing after workpiece table Surface hardness is still relatively low compared with ganoine thin film, cannot meet the demand of growing application conditions.On the other hand, when single Ground deposit ganoine thin film when, die life be able to extend, production efficiency is improved, manufacturing cost is minimized, But the defects of being commonly present hole and crackle in ganoine thin film provides path for Korrosionsmedium etched the matrix, reduces film Corrosion resistance, and higher using under loading condition, parent metal is easy to be plastically deformed, then the failure of film is Inevitably.
Patent of the present invention by low-temperature plasma nitridation technique hot die steel substrate surface prepare one layer of low temperature etc. from Sub- nitration case, then by cathode ion coating technology in nitridation layer surface depositing Al CrN coatings, to which low-temperature plasma nitrogen be made Change-AlCrN composite coatings.AlCrN coating surfaces are fine and close, and the mechanical properties such as hardness, thermal stability and impact resistance abrasiveness are compared It is improved in matrix, occurs a small amount of amorphous AlN phases in coating, be conducive to the refinement of sample crystallite dimension.Nitration case is Outermost AlCrN coatings provide powerful supporting role, eliminate the danger of stress concentration at coating/basal body interface, can be with Effectively avoid the premature failure of AlCrN coatings.
Invention content
Described in patent of the present invention low-temperature plasma nitridation with cathode ion plating compounding method refer to low temperature etc. from Depositing Al CrN coatings on the basis of son nitridation.The present invention adopts the following technical scheme that realization：Quenched place is carried out to base material first Reason, after it is polished and is mechanically polished, is cleaned by ultrasonic using acetone；By the way of low temperature nitriding, in temperature The low-temperature plasma Nitrizing Treatment of 10h is carried out when being 400 DEG C to base material, wherein the volume ratio of nitrogen and hydrogen is 2:1, nitrogen Throughput is 35mLmin-1, air pressure is 400-500Pa in stove, and substrate surface forms the nitration case that a layer thickness is 10 μm, applies Element between layer and matrix mutually diffuses to form good metallurgical binding；It, will be high finally when preparing AlCrN films on nitration case Pure Cr targets (99.9% purity) and high-purity AlCr targets (99.9% purity) are symmetrically installed at left and right sides of sample room, sample and the moon The distance between pole target be 200mm, fixed by holder and with the speed of 2rpm rotate, be passed through high-purity Ar gas, to matrix surface into Row arc light Bombardment and cleaning, wherein setting bias is -800V, and scavenging period 20min then passes to N2, by N2/ Ar gas flows It is 1 than control:1, carry out depositing Al CrN coatings, time 200min.
The main feature of the present invention：Patent of the present invention plates combination process to heat using low-temperature plasma nitridation-cathode ion Make mold steel surface and be modified processing, improves the mechanical property of sample by preparing AlCrN coatings, the addition of Al elements makes Sample obtains higher thermal stability and inoxidizability, so as to preferably cope with the extreme operating condition during mold work；It is logical It crosses and prepares low-temperature plasma nitration case and provide support for AlCrN coatings, eliminate the stress concentration at coating/basal body interface, keep away Exempt from AlCrN coatings prematurely to fail, veritably realizes the effective protection to hot-work die.
Description of the drawings
Fig. 1 low-temperature plasmas nitrogenize operating diagram
Fig. 2 cathode ions plate operating diagram
Fig. 3 low-temperature plasma nitration case surface topographies
Fig. 4 low-temperature plasma nitration case cross-section morphologies
Fig. 5 low-temperature plasma nitration case XRD analysis
The EDS analyses of Fig. 6 low-temperature plasma nitration cases
Fig. 7 low-temperature plasma nitridation+AlCrN coating morphologies
Fig. 8 low-temperature plasma nitridation+AlCrN coating cross-section morphologies
Fig. 9 low-temperature plasma nitridation+AlCrN coating XRD analysis
The EDS analyses of Figure 10 low-temperature plasma nitridation+AlCrN coatings
Specific implementation mode
(1) 1080 DEG C of oil quenchings are carried out to base material and 550 DEG C of high tempering is handled, and after heat treatment, it is ground Light and mechanical polishing are cleaned by ultrasonic 15min, to remove specimen surface grease and sundries with acetone；
(2) low-temperature plasma for carrying out 10h to base material at a temperature of 400 DEG C nitrogenizes, the volume ratio of nitrogen and hydrogen It is 2:1, nitrogen flow 35mLmin-1, air pressure is 400-500Pa in stove, and sample is cooled down 60-100min after the completion of nitriding；
(3) sample after nitrogenizing low-temperature plasma is placed in depositing device, high-purity Cr targets (99.9% purity) and height Pure AlCr targets (99.9% purity) are symmetrically installed at left and right sides of sample room, and the distance between sample and cathode target are 200mm, It is fixed by holder and is rotated with the speed of 2rpm, before the deposition, chamber is evacuated to 4 × 10-3Pa pressures of foundation below, and 450 DEG C are heated the sample to, Cr target arcs source is opened, sample is lost with the high bias voltage of -800V in argon plasma indoors It carves 20 minutes；
(4) Cr targets are closed, open AlCr targets, depositing Al CrN coatings, target arc current is 75A, by N2/ Ar gas flows It is 1 than control:1, N2Pressure maintains 2Pa, sedimentation time 200min；
(5) it is plated by SEM and XRD analysis low-temperature plasma nitration case and low-temperature plasma nitridation-cathode ion compound Surface-the cross-section morphology and chemical element of coating form.As shown in Figure 1, low-temperature plasma nitridation is divided into heat treatment, nitriding Processing and cooling three phases；As shown in Fig. 2, cathode ion plating be one kind in low-pressure gas discharging plasma environment into Capable physical gas phase deposition technology；As shown in Figure 3,4, nitridation layer surface is complete, the obvious shortcomings such as imporosity, crackle, in section On there are the diffusion regions apparent nitride layer, white layer (composite layer) and be made of martensite containing nitrogen, matrix mutually to expand with nitration case element It dissipates, forms good metallurgical binding；As shown in Figure 5,6, after nitridation, occurs N element in nitration case, and mainly with γ '-Fe4N and ε-Fe2-3The form of N two-phases exists；As shown in Figure 7,8, it for compared to nitration case, is deposited after low-temperature plasma nitridation AlCrN coatings are more fine and close, the layering of AlCrN layers apparent, nitration case and matrix occur in section；As shown in Figures 9 and 10, low The atomicity ratio of Al and Cr is about 67 in the plasma nitrided+AlCrN coatings of temperature：33, there is amorphous in X ray diffracting spectrum Phase, this is conducive to the refinement of sample crystallite dimension and the raising of mechanical property.

Claims (8)

1. a kind of hot die steel low-temperature plasma nitridation plates compounding method with cathode ion, it is characterised in that comprising as follows Step：
1) modifier treatment, mechanical polishing and cleaning are carried out to base material；
2) plasma nitrided layer is prepared on base material；
3) AlCrN films are prepared on nitration case.
2. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is that modifier treatment mode is 1080 DEG C of oil quenchings and the processing of 550 DEG C of high tempering in the step 1).
3. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is that the cleaning in the step 1) is the ultrasonic cleaning carried out using acetone, scavenging period 15min.
4. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is that nitride forms are low-temperature plasma nitriding in the step 2), and nitriding temperature is 400 DEG C, nitridation time 10h.
5. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is that base material is in N in the step 2)2And H2Mixed atmosphere in, wherein N2And H2Volume ratio be 2:1, N2Flow For 35mLmin-1, air pressure is 400-500Pa in stove.
6. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is that substrate surface forms the low-temperature plasma nitration case that a layer thickness is about 10 μm, coating and matrix in the step 2) Between element mutually diffuse to form good metallurgical binding.
7. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is, the high-purity Cr targets and high-purity AlCr targets that purity is 99.9% is used in the step 3), between sample and cathode target Distance is 200mm, is fixed by holder and is rotated with the speed of 2rpm.
8. hot die steel low-temperature plasma nitridation as described in claim 1 plates compounding method with cathode ion, special Sign is, high-purity Ar gas is passed through in the step 3), to matrix surface carry out arc light Bombardment and cleaning, wherein setting bias be- 800V, scavenging period 20min, then passes to N2, by N2The control of/Ar gas flow ratios is 1:1, depositing Al CrN coatings are carried out, Sedimentation time is 200min.
CN201810694421.7A 2018-06-29 2018-06-29 A kind of nitridation of hot die steel low-temperature plasma plates compounding method with cathode ion Pending CN108796443A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109371217A (en) * 2018-12-10 2019-02-22 江铃汽车股份有限公司 A kind of surface treatment method of cold punching die

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156912A1 (en) * 2007-05-30 2010-02-24 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool
CN103898445A (en) * 2014-04-18 2014-07-02 常州多晶涂层科技有限公司 Multilayer AlCrN cutting tool coating and preparation method thereof
CN104911552A (en) * 2015-06-25 2015-09-16 西安交通大学 Method for reinforcing surface of hot-extrusion die through cementation compounding
CN106011738A (en) * 2016-06-16 2016-10-12 常州普威特涂层有限公司 Surface plating composite coating process for die

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156912A1 (en) * 2007-05-30 2010-02-24 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool
CN103898445A (en) * 2014-04-18 2014-07-02 常州多晶涂层科技有限公司 Multilayer AlCrN cutting tool coating and preparation method thereof
CN104911552A (en) * 2015-06-25 2015-09-16 西安交通大学 Method for reinforcing surface of hot-extrusion die through cementation compounding
CN106011738A (en) * 2016-06-16 2016-10-12 常州普威特涂层有限公司 Surface plating composite coating process for die

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109371217A (en) * 2018-12-10 2019-02-22 江铃汽车股份有限公司 A kind of surface treatment method of cold punching die

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